US8143181B2 - Nonlinear optic glassy fiber, methods of making and applications of the same - Google Patents
Nonlinear optic glassy fiber, methods of making and applications of the same Download PDFInfo
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- US8143181B2 US8143181B2 US12/436,409 US43640909A US8143181B2 US 8143181 B2 US8143181 B2 US 8143181B2 US 43640909 A US43640909 A US 43640909A US 8143181 B2 US8143181 B2 US 8143181B2
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
- C03C13/04—Fibre optics, e.g. core and clad fibre compositions
- C03C13/041—Non-oxide glass compositions
- C03C13/043—Chalcogenide glass compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
- C03B37/022—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor from molten glass in which the resultant product consists of different sorts of glass or is characterised by shape, e.g. hollow fibres, undulated fibres, fibres presenting a rough surface
- C03B37/023—Fibres composed of different sorts of glass, e.g. glass optical fibres, made by the double crucible technique
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/80—Non-oxide glasses or glass-type compositions
- C03B2201/86—Chalcogenide glasses, i.e. S, Se or Te glasses
Definitions
- (1) represents the 1st reference cited in the reference list, namely, Chung I, Do J, Canlas C G, Weliky D P, Kanatzidis M G, Inorganic Chemistry 43 (9): 2762-2764 May 3 2004.
- the present invention relates generally to a process for producing an optical article, such as glass fiber or glassy or crystallized film, from crystal-glass phase material, which exhibit strong second harmonic generation (SHG) and waveguide performance, and the resultant materials and applications of same.
- an optical article such as glass fiber or glassy or crystallized film
- Second harmonic generation is a nonlinear optic process.
- SHG Second harmonic generation
- NLO nonlinear optic
- Silica fibers play a main role of optical switches, routers, splitters, modulators, and waveguidance in current optical communications and rapidly growing high speed broadband internet.
- its usefulness is greatly limited to be passive devices because of its lack of second-order nonlinearity. It is not an SHG NLO material. Therefore, there have been tremendous efforts to induce SHG in glass using specific treatments such as thermal electric field poling, electron beam irradiation, and so on. It does need complicated processes and any induced SHG is much weaker than normal NLO crystals.
- oxide nonlinear optic materials are poorer than chalcogenide species because chalcogen atoms (S, Se, Te) are more polarizable than oxygen.
- Chalcogenide or chalcopyrite compounds exhibited excellent SHG response and broad transparency through infrared region.
- CdGeAs 2 ranks first in the SHG susceptibility before the introduction of APSe 6 and A 2 P 2 Se 6 by the inventors as set forth below.
- CdGeAs 2 however is very limited.
- the compound consists of toxic elements such as Cd and As, and it is very difficult to grow single crystals.
- the crystals show anisotropic thermal expansion allowing cracking. Due to the small band gap, its transparency range is only 2.4 to 17 ⁇ m, consequently Nd:YAG and GaAs laser are unavailable for use in conjunction with CdGeAs 2 and only CO 2 laser can be used.
- the present invention in one aspect, relates to a process for producing an optical glass fiber from crystal-glass phase material.
- the process includes the steps of providing a molten crystal-glass phase material in a container, wherein the temperature of the molten crystal-glass phase material is at or above the melting temperature of the molten crystal-glass phase material, T m , to allow the molten crystal-glass phase material is in liquid phase; cooling the molten crystal-glass phase material such that the temperature of the molten crystal-glass phase material, T 1 , is reduced to below T m such that the molten crystal-glass phase material is changed from the liquid phase to a viscous melt; and pulling a glass fiber of the crystal-glass phase material from the viscous melt, wherein T 1 satisfies the following relationship: T v ⁇ T 1 ⁇ T m , and T v being the temperature at which the vitrification of the viscous melt of the crystal-glass phase material occurs, and wherein the crystal-glass phase material is characterized by having
- the crystal-glass phase material comprises one or more noncentrosymmetric crystal-glass phase-change materials, wherein the noncentrosymmetric crystal-glass phase-change materials comprise chalcophosphate and chalcogenide materials that are structurally one-dimensional.
- the chalcophosphate and chalcogenide materials that are structurally one-dimensional each comprise one or more compounds of
- the chalcophosphate and chalcogenide materials that are structurally one-dimensional each comprise at least a part of a polymeric [PSe 6 ⁇ ] chain, an extended helical chain of
- the step of providing a molten crystal-glass phase material in a container includes the steps of mixing at least one of the compounds in polar organic solvents such as anhydrous hydrazine solution to form a mixture; and heating the mixture so that it melts into liquid phase.
- polar organic solvents such as anhydrous hydrazine solution
- the reversible thermal behavior of the crystal-glass phase material is that upon heating, the crystal-glass phase material crystallizes first and then subsequently melts when the temperature is at or above the melting temperature of the molten crystal-glass phase material, T m , while upon cooling, the vitrification of the viscous melt of the crystal-glass phase material occurs instead of the recrystallization of the crystal-glass phase material.
- the T m is less than 300° C.
- the temperature during said pulling ranges from about 220° C. to 280° C.
- the glass fiber of the crystal-glass phase material made by the process according to the present invention exhibits intrinsic second-order nonlinear optic properties and useable in a nonlinear optic or ferroelectric article.
- the present invention in another aspect, relates to a process for producing an optical film from crystal-glass phase material.
- the process includes the steps of mixing at least one of crystal-glass phase materials and the compounds in anhydrous hydrazine to form a solution; applying the solution to a substrate to form a film of the solution over a surface of the substrate; and annealing the film of the solution over a surface of the substrate at a first temperature sufficiently high to remove the hydrazine to allow a film of the at least one of crystal-glass phase materials to be formed in glass phase, wherein the crystal-glass phase material is characterized by having a reversible thermal behavior.
- the crystal-glass phase material comprises one or more noncentrosymmetric crystal-glass phase-change materials, wherein the noncentrosymmetric crystal-glass phase-change materials comprise chalcophosphate and chalcogenide materials that are structurally one-dimensional.
- the chalcophosphate and chalcogenide materials that are structurally one-dimensional each comprise one or more compounds of
- the chalcophosphate and chalcogenide materials that are structurally one-dimensional each comprise at least a part of a polymeric [PSe 6 ⁇ ] chain, an extended helical chain of
- the first temperature during said annealing ranges from about 100° C. to 130° C.
- the glassy film of the crystal-glass phase material made by the process exhibits intrinsic second-order nonlinear optic properties and useable in a nonlinear optic or ferroelectric article.
- the process further includes a step of further annealing the glassy film at a second temperature about twice higher than said first temperature to allow the glassy film to crystallize into a crystallized film.
- the second temperature during said further annealing ranges from about 250° C. to 300° C.
- the time of said further annealing ranges from about 2 to 15 minutes.
- the crystallized film of the crystal-glass phase material made by the process exhibits intrinsic second-order nonlinear optic properties and useable in a nonlinear optic or ferroelectric article.
- the present invention in yet another aspect, relates to a glass fiber made from one or more crystal-glass phase material, wherein the crystal-glass phase material is characterized by having a reversible thermal behavior.
- the crystal-glass phase material comprises one or more noncentrosymmetric crystal-glass phase-change materials, wherein the noncentrosymmetric crystal-glass phase-change materials comprise chalcophosphate and chalcogenide materials.
- the present invention in a further aspect, relates to a glassy or crystallized film made from one or more crystal-glass phase material, wherein the crystal-glass phase material is characterized by having a reversible thermal behavior.
- the crystal-glass phase material comprises one or more noncentrosymmetric crystal-glass phase-change materials, wherein the noncentrosymmetric crystal-glass phase-change materials comprise chalcophosphate and chalcogenide materialsthat are structurally one-dimensional.
- the chalcophosphate and chalcogenide materials that are structurally one-dimensional each comprise one or more compounds of
- the chalcophosphate and chalcogenide materials that are structurally one-dimensional each comprise at least a part of a polymeric [PSe 6 ⁇ ] chain, an extended helical chain of
- the present invention in yet another aspect, relates to a glassy or crystal compound made from one or more noncentrosymmetric crystal-glass phase-change materials.
- the noncentrosymmetric crystal-glass phase-change materials each comprise chalcophosphate and chalcogenide materials that are structurally one-dimensional.
- the chalcophosphate and chalcogenide materials that are structurally one-dimensional each comprise one or more compounds of
- the chalcophosphate and chalcogenide materials that are structurally one-dimensional each comprise at least a part of a polymeric [PSe 6 ⁇ ] chain, an extended helical chain of
- the glassy or crystal compounds of the present invention can be used in a nonlinear optic or ferroelectric article.
- FIG. 1 illustrates structure of the polymeric anions
- FIG. 2 illustrates a process of preparation of KPSe 6 glassy optical fiber from its melt according to one embodiment of the present invention.
- FIG. 3 shows (A) a representative photograph of a KPSe 6 optical fiber showing remarkable flexibility, which is made according to one embodiment of the present invention; (B) A representative SEM image of a KPSe 6 fiber showing thickness uniformity at 50.0 ⁇ m and surface smoothness; (C) X-ray diffraction ring patterns of pristine glassy (left) and annealed fiber (right) confirming their amorphous and crystalline nature, collected by STOE II single crystal diffractometer (Ag K ⁇ ); and (D) X-ray diffraction patterns of the pristine glassy (upper) and annealed fibers regenerated from the ring patterns. Note that the Bragg peaks from the annealed fiber are successfully indexed, indicative of the restoration of crystal structure on the fiber. (hkl) index on the major peak is presented.
- FIG. 4 illustrates (A) a Raman spectra of KPSe 6 crystal, bulk glass, pristine glassy fiber, and annealed fiber.
- B Pair distribution function (PDF) analysis for the glassy fiber, bulk glass, and crystalline powders. Fibers with different thickness at d ⁇ 50 ⁇ m and d ⁇ 200 ⁇ m were examined for comparison. Theoretical fit based upon single crystal structure refinement is plotted as black circles. The first peak at 2.3 ⁇ corresponds to interatomic correlations of P—Se and Se—Se bonds, and the second peak at 3.7 ⁇ K . . . Se and second neighbouring Se . . . Se.
- FIG. 5 illustrates a Raman spectra and pair distribution function analysis for the glass powder of
- KPSe 7 “KPSe 7 ”, “KPSe 8 ”, and “KPSe 9 ”.
- FIG. 6A illustrates a representative SEM image of RbPSe6 glassy thin film showing clean surface morphology of spin-coated thin film.
- FIG. 6B illustrates X-ray diffraction patterns of the pristine RbPSe6 glass film on a Si wafer substrate (middle) and the crystallized film after annealing at 250° C. for 5 min, compared with theoretical simulation patterns based on RbPSe 6 single crystal diffraction refinement. Major peaks are indexed.
- FIG. 7 illustrates relative size to SHG intensities of KPSe6 crystal (squares) and AgGaSe2 (circles).
- FIG. 8 illustrates particle size to SHG intensities diagram of crystalline RbPSe 6 showing type-I phase-matching.
- FIG. 9 illustrates SHG response of KPSe 6 crystal and powdered glass relative to AgGaSe 2 crystal over a wide range of wavelengths.
- FIG. 10 illustrates (A) SHG response of K 2 P 2 Se 6 relative to AgGaSe 2 over a wide range of wavelengths. (B) Particle size to SHG intensities diagram of crystalline K 2 P 2 Se 6 showing type-I phase-matching.
- FIG. 11 illustrates SHG response of
- FIG. 12 illustrates Far-IR (red line)/mid IR (green line)/vis (blue line) absorption spectra of crystalline K 2 P 2 Se 6 .
- Wide transparent range of crystalline K 2 P 2 Se 6 above the absorption band at 19.8 ⁇ m at far-IR region through mid-IR to 0.596 ⁇ m at visible region is shown.
- FIG. 13 illustrates SHG waveguidance mode response of
- FIG. 14 illustrates DFG responses in a wide range of wavelengths generated by a KPSe 6 glassy fiber.
- FIG. 15 illustrates the relative SHG intensities measured from 620 to 805 nm for the pristine glassy and annealed fibers, representing remarkable enhancement of the SHG response after heat treatment at 260° C. for 3 min.
- FIG. 16 a illustrates waveguided NLO response measurement of RbPSe 6 thin film.
- FIG. 16 b illustrates the waveguided SHG response transmitted through 1.25 cm long RbPSe 6 thin film.
- FIG. 17 shows images of visible green, red, and orange light converted from invisible near IR laser.
- FIG. 18 illustrates the waveguided DFG response transmitted through 1.25 cm long RbPSe 6 thin film.
- FIG. 19 illustrates ferroelectric hysteresis of RbPSe 6 crystalline thin film made according to one embodiment of the present invention.
- “around”, “about” or “approximately” shall generally mean within 20 percent, preferably within 10 percent, and more preferably within 5 percent of a given value or range. Numerical quantities given herein are approximate, meaning that the term “around”, “about” or “approximately” can be inferred if not expressly stated.
- SEM scanning electron microscope
- the present invention in one aspect, relates to a general fabrication method for second harmonic generating (SHG) optical glassy fiber using noncentrosymmetric crystal-glass phase-change materials.
- the optical glassy fibers exhibited strong waveguided second harmonic generation response along the fiber in the IR region.
- the nonlinear optical response was there without the application of electric fields (poling) to the fibers.
- the d eff value is comparable to that of commercially used crystals KNbO 3 and KTiOPO 4 (KTP). It also generated a frequency mixing signal of difference frequency generation (DFG) continuously in a wide range of visible/near IR region.
- DFG difference frequency generation
- Annealing thin glassy films gave high performing crystalline films that exhibit strong NLO responses and ferroelectricity. These materials are of interest for broad applications as a frequency converters and waveguiding fibers. By adding excess chalcogens to APSe 6 compounds, new series of NLO glasses are prepared. They are also fiber and thin film processable.
- the approach to fabricate NLO glassy fibers is to use crystal-glass phase-change materials that adopt noncentrosymmetric space groups.
- Crystal-glass phase-change materials made of chalcophosphate and chalcogenide materials easily form glassy phases and restore its crystal structure.
- Recent studies by the inventors demonstrated that the glassy state still retains a substantial local structure but only loses long-range crystallographic order. In this case, the noncentrosymmetric arrangement in the crystal can be preserved to a large degree in the glassy form.
- the NLO susceptibility of glass would be smaller than that of the corresponding crystal, it must be superior to that of conventional glass that needs to be treated by a specific poling technique.
- the glassy fibers are only mildly poled with laser, they exhibit dramatically enhanced SHG performance.
- it was dissolved crystal-glass phase-change material that adopt noncentrosymmetric space groups in polar organic solvents, and glassy thin film was prepared by a spin coating. Resulting glassy films can be easily transformed to crystalline films. Both crystalline and glassy thin films showed strong NLO response. They are also ferroelectric.
- the corresponding glassy phases (as mentioned above) also exhibited significant SHG response without poling, of which SHG susceptibility is comparable to that of commercial KTiOPO 4 (KTP) and KNbO 3 .
- Both the crystalline and glassy phases have a wide transparency range from 0.6 ⁇ 0.7 ⁇ m to 19 ⁇ 20 ⁇ m, dependent upon band gaps.
- K 2 P 2 Se 6 showed isotropic thermal expansion, which is a key issue for crystal growing. Those compounds are easily processable to fibers or thin films that are favored for practical applications.
- FIGS. 1-19 Various unique features of the present invention will be made as to the embodiments of the present invention in conjunction with the accompanying drawings in FIGS. 1-19 .
- Electron Microscopy Semiquantitative analyses of the compounds were performed with a JEOL JSM-35C scanning electron microscope (SEM) equipped with a Tracor Northern energy dispersive spectroscopy (EDS) detector.
- SEM scanning electron microscope
- EDS Tracor Northern energy dispersive spectroscopy
- Solid-State UV-Vis spectroscopy Optical diffuse reflectance measurements were performed at room temperature using a Shimadzu UV-3101 PC double-beam, double-monochromator spectrophotometer operating in the 200-2500 nm region.
- Raman Spectroscopy Raman Spectroscopy. Raman spectra were recorded on a Holoprobe Raman spectrograph equipped with a CCD camera detector using 633 nm radiation from a HeNe laser for excitation and a resolution of 4 cm ⁇ 1 . Laser power at the sample was estimated to be about 5 mW, and the focused laser beam diameter was ca. 10 ⁇ m. A total of 128 scans was sufficient to obtain good quality spectra.
- FT-IR spectra were recorded as solids in a CsI or KBr matrix. The samples were ground with dry CsI or KBr into a fine powder and pressed into translucent pellets. The spectra were recorded in the far-IR region (600-100 cm ⁇ 1 , 4 cm ⁇ 1 resolution) and mid-IR region (500-4000 cm ⁇ 1 , 4 cm ⁇ 1 resolution) with the use of a Nicolet 740 FT-IR spectrometer equipped with a TGS/PE detector and silicon beam splitter.
- DTA Differential Thermal Analysis
- Nonlinear Optical Property Measurements The frequency-tripled output (355 nm) of a passive-active mode-locked Nd:YAG laser with a pulse width of about 30 ps and a repetition rate of 10 Hz to pump an optical parametric amplifier (OPA) were used.
- OPA optical parametric amplifier
- the OPA generates vertically polarized pulses in the range 400 ⁇ 3,156 nm.
- the incident laser pulse of 0.2 mJ was focused onto the proximal surface of a fiber with a spot 300 ⁇ m in diameter using a 3 cm focal-length parabolic lens.
- the diameter of this fiber was about 122 ⁇ 2 ⁇ m and its length is 10 mm.
- the corresponding instantaneous peak power is about 6.7 MW.
- the time-average input fluence is only 2.8 W cm ⁇ 2 well below the damage threshold for chalcogenide compounds.
- the corresponding peak fluence is about 9 GW cm ⁇ 2 that can induce third harmonic response of the test material, no third-harmonic generation was detected, even with an extended collection time.
- the negligible ⁇ (3) response from APSe 6 was independently confirmed through the absence of a Z-scan response.
- the SHG signals were collected in a waveguide mode and dispersed with a Spex Spec-One 500 M spectrometer coupled to a nitrogen-cooled CCD camera. Since the monitoring range in the wavelength is rather wide, no filter was used but it was made sure that other optical components did not generate additional SHG signals.
- the SHG response from powder samples was measured using a reflection geometry under similar conditions.
- This example illustrates composition(s) of matters or compounds that were used in various embodiments of the present invention.
- KPSe 6 possesses PSe 4 tetrahedra condensed with polyselenide linkages to give the polymeric [PSe 6 ⁇ ] chain.
- the length of Se chain can be extended up to Se 10 by adding excess Se to KPSe 6 , and the glassy KPSe z (6 ⁇ z ⁇ 12) are obtained, as shown in FIG. 1B .
- K 2 P 2 Se 6 has infinitely extended helical chains of
- APSe 6 and A 2 P 2 Se 6 are only examples of free-standing polymeric chalcophosphate with no coordinating metals.
- This example describes methods of making compounds, pure crystal and glass, that were used in various embodiments of the present invention.
- EDS Energy dispersive spectroscopy
- the crystalline compounds were air-stable for at least a week and stable under polar solvents such as DMF, N-methylformamide, methyl and ethyl alcohol and H 2 O.
- This example describes a process of making glass fiber from crystal-glass phase material according to one embodiment of the present invention.
- the process includes the steps of providing a molten crystal-glass phase material in a container, wherein the temperature of the molten crystal-glass phase material is at or above the melting temperature of the molten crystal-glass phase material, T m , to allow the molten crystal-glass phase material is in liquid phase; cooling the molten crystal-glass phase material such that the temperature of the molten crystal-glass phase material, T 1 , is reduced to below T m such that the molten crystal-glass phase material is changed from the liquid phase to a viscous melt; and pulling a glass fiber of the crystal-glass phase material from the viscous melt, wherein T 1 satisfies the following relationship: T v ⁇ T 1 ⁇ T m , and T v being the temperature at which the vitrification of the viscous melt of the crystal-glass phase material occurs, and wherein the crystal-glass phase material is characterized by having a reversible thermal behavior.
- crystal-glass phase-change materials The reversible thermal behavior of crystal-glass phase-change materials is that upon heating the crystal-glass phase-change material crystallizes from glassy phase first and then subsequently melts into a viscous melt when the temperature is at or above the melting temperature of the crystal-glass phase-change material, but upon cooling only vitrification of the viscous melt occurs, rather than recrystallization of the crystal-glass phase-change material.
- a viscous melt of APSe 6 and A 2 P 2 Se 6 is prepared and contained in a container at a temperature at or above the melting temperature at step 202 in liquid phase. Then at step 204 , the viscous melt is cooled from the liquid phase but the temperature is kept between vitrification and the melting point, here in the range of about 230-280° C., where a continuous viscosity-temperature dependence exists that makes pulling, even high-speed pulling, or drawing possible of fiber from the viscous melt.
- a glass fiber 206 is pulled from the viscous melt, which is then at Step 208 placed under vacuum in a quartz tube at 8-900° C. for about 1-2 minutes and subsequent quenching to room temperature. APSe z glassy fibers were also obtained in a similar way.
- the processing temperature of the chalcogenide fibers is considerably lower than that of oxides for the existing technologies.
- silica fiber requires approximately 2,000 K for softening Fibers with thickness ranging from a few to a hundred micrometers, having remarkable flexibility, could be prepared ‘by hand’ as shown in FIG. 2A , or by machine for high speed pulling as known in the art, with lengths approaching a meter.
- SEM scanning electron microscope
- the Raman spectrum of crystalline KPSe 6 at room temperature shows major shifts at 220 (s), 231 (m), and 246 (m) cm ⁇ 1 , as shown in FIG. 4A .
- the shift at 220 cm ⁇ 1 is unambiguously assigned to the PSe 4 stretching mode by comparing with the A g stretching mode of the T d symmetry of [PSe 4 ] 3 ⁇ ligand.
- the shifts at 231 and 246 cm ⁇ 1 can be assigned to antisymmetric and symmetric Se—Se stretching modes of the diselenide group, respectively.
- the PDF of bulk glass and glassy fiber shows well-defined correlations up to ⁇ 8 ⁇ with the maxima at 2.3 ⁇ (P—Se and Se—Se bonds) and 3.7 ⁇ (K . . . Se and the second neighbour Se . . . Se distances) being very close to those of the crystalline phase. Above ⁇ 8 ⁇ , the PDFs decay rapidly to zero, indicating the loss of the long-range order. The PDF result is consistent with that of K 2 P 2 Se 6 . Those observations support the facile restoration of the crystal structure from the amorphous state at the reversible crystal-glass phase transition.
- the Raman spectrum of annealed fiber is same as that of bulk crystal, confirming the recovery of crystalline structure in the fiber form, consistent with the X-ray powder diffraction results (See FIGS. 3C and 3D ). However, it is found that the annealed fiber consists of grain boundaries with macroscopic sizes, implying a polycrystalline structure in the extended dimension.
- This example describes a process of making thin film from crystal-glass phase material according to one embodiment of the present invention.
- the process includes the steps of mixing at least one of crystal-glass phase materials and the compounds in anhydrous hydrazine to form a solution; applying the solution to a substrate to form a film of the solution over a surface of the substrate; and annealing the film of the solution over a surface of the substrate at a first temperature sufficiently high to remove the hydrazine to allow a film of the at least one of crystal-glass phase materials to be formed in glass phase, wherein the crystal-glass phase material is characterized by having a reversible thermal behavior.
- the second temperature during said further annealing ranges from about 250° C. to 300° C.
- the time of said further annealing ranges from about 2 to 15 minutes.
- the crystallized film of the crystal-glass phase material made by the process exhibits intrinsic second-order nonlinear optic properties.
- APSe 6 , A 2 P 2 Se 6 , and APSe z (6 ⁇ z ⁇ 12) are dissolved in anhydrous hydrazine forming concentrated solutions. These solutions can be readily spin-coated or drop-casted into films of various thicknesses on a substrate. The films are then annealed at 100-130° C. to remove the hydrazine to give orange to red glassy films depending on thickness. A representative glassy thin film having the clean surface and well defined edge is shown in FIG. 5 . Crystalline APSe 6 and A 2 P 2 Se 6 films are obtained by further annealing the corresponding glassy films for about 5-10 min at about 250-300° C. FIG. 6 shows the thin film X-ray diffraction patterns of the pristine and crystallized RbPSe 6 film, confirming amorphous nature of a glassy film and fully recovered crystalline structure after annealing at 250° C. for about 5 min.
- This example describes nonlinear optical properties of crystalline and glassy phases of APSe 6 and A 2 P 2 Se 6 , and APSe z (6 ⁇ z ⁇ 12) glasses according to one embodiment of the present invention and use of them.
- Input light pulses were generated by an optical parametric amplifier driven by a Nd:YAG pulsed laser at 355 nm with a repetition rate of 10 Hz.
- the responses increase with particle size, indicating type-I phase-matching in the observation range, as shown in FIG. 8 .
- These values for APSe 6 compounds are the highest among phase-matchable inorganic NLO materials with band gaps over 1.0 eV. Note that the narrower optical band gap causes the poorer laser damage threshold while shrinking the range of optical transparency window.
- K 2 P 2 Se 6 generated strong double frequency (i.e. SHG) signals from the fundamental idler beam.
- SHG intensity of K 2 P 2 Se 6 showed a maximum at 789 nm which is about 50 times larger than that of AgGaSe 2 in the same wavelength.
- AgGaSe 2 showed a SHG maximum at 890 nm and in this wavelength the corresponding response of K 2 P 2 Se 6 was 20-fold higher, as shown in FIG. 10A .
- KPSe z (6 ⁇ z ⁇ 12) glassy compound series exhibited significant innate SHG response like APSe 6 and A 2 P 2 Se 6 glasses, as shown in FIG. 11 .
- APSe 6 and A 2 P 2 Se 6 are crystal-glass phase-change materials and their crystalline phases crystallize in the noncentrosymmetric space group, and their glassy phases are observed to possess largely preserved local structural motifs. In this regard, large SHG response of glasses could be understood.
- “KPSe 7 ”, “KPSe 8 ”, and “KPSe 9 ” are totally different class of materials from APSe 6 and A 2 P 2 Se 6 glass family in that APSe z does not have noncentrosymmetric crystalline counterparts.
- LWIR long wave IR
- NIR near IR
- the mid-IR transmittance spectrum showed little absorption from 505 cm ⁇ 1 (19.8 ⁇ m) to 4000 cm ⁇ 1 (2 ⁇ m). There is no light absorption below the band gap transition suggesting uninterrupted light transmission in the compound.
- the optical transparency extends over to its absorption edge of 2.08 eV (596 nm) in the visible region. Above 19.8 ⁇ m in the far-IR region, the compound exhibited a complex set of absorptions, consistent with its Raman and far-IR spectra.
- Optical transparency is a key feature for materials aimed at NLO applications. For example, the important NLO material for IR applications, AgGaSe 2 , shows LWIR transmission up to 17 ⁇ m.
- This example describes nonlinear optical properties of glassy fiber according to one embodiment of the present invention and use of them.
- Phase-change materials are of great interest as emerging technologies including rewritable optical media and the development of nonvolatile phase-change memory. Conversion between the crystalline and glassy states can be driven by applying a voltage or heat, or by irradiating with an appropriate laser.
- the annealed fiber exhibited over 10 times larger SHG intensities compared to the pristine glassy fiber in a wide range of wavelengths, as shown in FIG. 15 .
- this enhancement is still a factor of 10 below the SHG intensity changes between the glassy and crystalline powders shown in FIGS. 7 and 8 .
- This deficit most likely arises from partial cancellation from random distributions of macroscopic grain boundaries with various polarization directions.
- Other possible mechanism could be random phase matching (RPM) since SHG intensity arising from RPM increases linearly with the NLO medium size.
- alkali chalcophosphates are compositionally very flexible.
- K 2 P 2 Se 6 substituting appropriate amount of other alkali metals, Tl, Ag, or Cu for K, or S for Se, enable to tune the band gap, keeping the structure, crystal-glass phase-change behavior, and nonlinear optic property.
- Substitution of Tl, Ag, or Tl can enhance the air/moisture stability of the materials and meet the condition for specific application conditions.
- This example describes nonlinear optical properties of glassy and crystalline thin film according to one embodiment of the present invention and use of them.
- RbPSe 6 is chosen as an exemplary example. It was tested spin-coated glassy thin film and crystalline thin film by annealing at 260° C. for 3 min. Glassy thin film showed significant SHG response at near IR region. The annealed film showed remarkably enhanced NLO properties. Being careful to precisely align the film with the laser path, in a set up as shown in FIG. 16A , the tuneable incident beam was focused onto proximal edge of the film, and ongoing light was collected from the distal end.
- RbPSe6 film acted as a frequency convertor in a waveguide mode. It produced continuously tuneable SHG signal over a wide range of wavelengths (625-768 nm), as shown in FIG. 16B . The deviation of SHG intensities result from the same reason as the crystalline, bulk glass and fiber samples as described above.
- FIG. 17 clearly showed strong waveguided SHG visible green, red and orange light converted from invisible near IR, confirming the continuous IR tuneability of RbPSe6 NLO thin film.
- the RbPSe 6 thin film successfully generated continuously tuneable near-IR light by DFG, as shown in FIG. 18 .
- This example describes ferroelectric properties of glass fiber, glassy and crystalline thin film according to one embodiment of the present invention and use of them.
- Ferroelectricity is symmetry dependent property as is SHG. Noncentrosymmetric arrangement of the crystal structure is prerequisite.
- the title materials readily form glassy fibers and thin films; and they can be converted to crystalline form.
- thin film preparation of ferroelectric materials is one of the most challenging problem in this field.
- it was used crystalline RbPSe 6 thin film that was converted from spin-coated amorphous film to measure ferroelectric behavior, the measured ferroelectric hysteresis of which is shown in FIG. 19 .
- This example describes some applications of glass fiber, glassy and crystalline thin film according to various embodiments of the present invention.
- Optical fibers exhibiting large second-order nonlinearity made according to various embodiments of the present invention can be used in frequency converter, wave mixer, optical switches, modulators, routers, splitters for wavelength-division-multiplexed (WDM) networks and optical microscopy and greatly improve their performance.
- WDM wavelength-division-multiplexed
- They can also be used in remote sensing, optical computing, molecular spectroscopy, atmospheric monitoring, ultra-sensitive detection, pollution monitoring, atmospheric chemistry, chemical and biological warfare detection (ppb levels), noninvasive medical diagnosis by breath analysis, and ultrasensitive detection of explosives down to ppt levels using cavity ring-down spectroscopy.
- Chalcogenide glasses have excellent optical transparency, mechanical flexibility, and high index of reflection, which makes them as promising candidates for photonic crystal fibers and planar waveguides.
- Ferroelectricity, pyrroelectricity, and piezoelectricity applications of crystalline and glassy bulk compounds and thin films and glassy fibers are also possible.
- the present invention provides two novel approaches on how to create stable NLO glass fibers and thin films.
- noncentrosymmetric phase-change materials can be used to quench an NLO-active glass phase from which fibers with stable SHG properties can be drawn.
- Glassy thin film can be conveniently converted by heat treatment at low temperature to form high quality corresponding crystalline thin film.
- APSe 6 glass fibers in certain embodiments possess intrinsic, switchable second-order NLO properties with the strongest response known for glasses.
- the approach disclosed here is an example of combining apparently unrelated properties (NLO+phase-change behaviour) to create new functional materials. This finding opens up the possibility of creating active, all-optical, broadband networks that independently modulate frequency, with no additional NLO or electronic devices. It was further showed that glassy thin films of those materials can be conveniently spin-coated and they are second-order NLO active. Those materials are also ferroelectric.
- noncentrosymmetric chalcogenide compounds can provide wide range of new NLO-active glasses. Those materials also could be ferro-, pyro-, and piezoelectric.
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Abstract
Description
-
- A1-xA′xPSe6S6-y (A, A′=K, Rb, Tl, Ag, Cu; 0≦x<1; 0≦y<6), A2-xA′xP2Se6S6-y (A, A′=K, Rb, Cs, Tl, Ag, Cu; 0≦x<1; 0≦y<6), and A1-xA′xPSez (A, A′=K, Rb, Cs, Tl, Ag, Cu; 0≦x<1; 6<z<12).
-
- A1-xA′xPSe6S6-y (A, A′=K, Rb, Tl, Ag, Cu; 0≦x<1; 0≦y<6), A2-xA′xP2Se6S6-y (A, A′=K, Rb, Cs, Tl, Ag, Cu; 0≦x<1; 0≦y<6), and A1-xA′xPSez (A, A′=K, Rb, Cs, Tl, Ag, Cu; 0≦x<1; 6<z<12).
-
- A1-xA′xPSe6S6-y (A, A′=K, Rb, Tl, Ag, Cu; 0≦x<1; 0≦y<6), A2-xA′xP2Se6S6-y (A, A′=K, Rb, Cs, Tl, Ag, Cu; 0≦x<1; 0≦y<6), and A1-xA′xPSez (A, A′=K, Rb, Cs, Tl, Ag, Cu; 0≦x<1; 6<z<12).
-
- A1-xA′xPSe6S6-y (A, A′=K, Rb, Tl, Ag, Cu; 0≦x<1; 0≦y<6), A2-xA′xP2Se6S6-y (A, A′=K, Rb, Cs, Tl, Ag, Cu; 0≦x<1; 0≦y<6), and A1-xA′xSez (A, A′=K, Rb, Cs, Tl, Ag, Cu; 0≦x<1; 6<z<12).
By introducing different combinations of idler and signal beams, the KPSe6 glass fiber successfully generated continuously tuneable near-IR light by DFG, as shown in
-
- 1) a general preparation approach was invented in an inexpensive and convenient way to produce optical glassy fibers and thin films exhibiting strong intrinsic SHG and ferroelectricity using non-centrosymmetric chalcophosphate materials;
- 2) the fibers show good wave-mixing performance (difference harmonic generation) without the need for poling;
- 3) the fibers demonstrate function in waveguide mode in the visible and the near IR region;
- 4) the APSe6 and A2P2Se6 glassy fibers are remarkably flexible;
- 5) the glassy thin films are second order NLO active and ferroelectric;
- 6) the glassy film can be easily converted to high quality crystalline films by heat treatment; and
- 7) a general preparation approach was invented to make new NLO-active bulk glasses and glassy fibers by adding excess chalcogens to noncentrosymmetric chalcogenide materials.
- (1) APSe(6) (A=K, Rb, and Cs): Polymeric selenophosphates with reversible phase-change properties Author(s): Chung I, Do J, Canlas C G, Weliky D P, Kanatzidis M G, Inorganic Chemistry 43 (9): 2762-2764 May 3 2004.
- (2)
Helical Polymer 1/∞[P2Se6 2−]: Strong Second Harmonic Generation Response and Phase-Change Properties of Its K and Rb Salts Chung, I.; Malliakas, C. D.; Jang, J. I.; Canlas, C. G.; Weliky, D. P.; Kanatzidis, M. G., J. Am. Chem. Soc.; (Article); 2007; 129(48); 14996-15006. - (3) Xu, W.; Blazkiewicz, P.; Fleming, S. Adv. Mater. 2001, 13, 1014.
- (4) Corbari, C.; Kazansky, P. G.; Slattery, S. A.; Nikogosyan, D. N. Appl. Phys. Lett. 2005, 86, 071106.
- (5) Nakayama, Y.; Pauzauskie, P. J.; Radenovic, A.; Onorato, R. M.; Saykally, R. J. Liphardt, J.; Yang, P. Nature, 2007, 447, 1098.
- (6) Tong, L.; Gattass, R. R.; Ashcom, J. B.; He, S.; Lou, J.; Shen, M.; Maxwell, I.; Mazur, E. Nature, 2003, 426, 816.
- (7) Choy, M. M.; Byer, R. L.,
Physical Review B 1976, 14, (4), 1693. - (8) Nikogosyan, D. N., Nonlinear optical crystals: a complete survey. Springer-Science: New York, 2005;
- (9) Knight, J. C. Nature, 2003, 424, 847.
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US10690992B2 (en) * | 2017-04-05 | 2020-06-23 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Chalcogenide glass waveguides for refractive non-mechanical beam steerer |
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US11679980B2 (en) | 2018-06-20 | 2023-06-20 | Northwestern University | Lithium-containing chalcophosphates for thermal neutron detection |
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